Monoazo dyestuffs

ABSTRACT

Monoazo dyestuffs which, in the form of the free acid, correspond to the formula ##STR1## in which X 1  and X 2  denote chlorine, bromine or trifluoromethyl, 
     R 1  denotes hydrogen or C 1  -C 8  -alkyl, which can be substituted by hydroxyl, 
     R 2  denotes hydrogen, C 1  -C 4  -alkoxy-C 1  -C 4  -alkyl, C 1  -C 13  -alkyl, phenyl which is optionally substituted by methyl, ethyl, chlorine, methoxy or ethoxy, benzyl, phenethyl, cyclohexyl or methylcyclohexyl, 
     R 3  denotes a direct bond, methylene, ethylene, methyleneoxy, methyleneoxycarbonyl, methyleneoxycarbonylamino, --O--, --NH--, aminomethylene or aminoethylene, 
     R 4  denotes hydrogen, methyl, methoxy or ethoxy, 
     R 5  and R 6  denote C 1  -C 4  -alkyl, which can be further substituted by cyano, chlorine, C 1  -C 4  -alkoxy, C 1  -C 4  -alkoxycarbonyloxy, C 1  -C 4  -alkylcarbonyloxy or phenylaminocarbonyloxy, benzyl or phenethyl, 
     R 7  denotes hydrogen or C 1  -C 4  -alkyl, and 
     R 8  and R 9  denote hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl or cyano, 
     a process for their preparation and their use for dyeing natural and synthetic fibre materials.

The invention relates to monoazo dyestuffs which, in the form of the free acid, correspond to the formula ##STR2## in which X₁ and X₂ denote chlorine, bromine or trifluoromethyl,

R₁ denotes hydrogen or C₁ -C₈ -alkyl, which can be substituted by hydroxyl,

R₂ denotes hydrogen, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, C₁ -C₁₃ -alkyl, phenyl which is optionally substituted by methyl, ethyl, chlorine, methoxy or ethoxy, benzyl, phenethyl, cyclohexyl or methylcyclohexyl,

R₃ denotes a direct bond, methylene, ethylene, methyleneoxy, methyleneoxycarbonyl, methyleneoxycarbonylamino, -O-, -NH-, aminomethylene or aminoethylene,

R₄ denotes hydrogen, methyl, methoxy or ethoxy,

R₅ and R₆ denote C₁ -C₄ -alkyl, which can be further substituted by cyano, chlorine, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxycarbonyloxy, C₁ -C₄ -alkylcarbonyloxy or phenylaminocarbonyloxy, benzyl or phenethyl,

R₇ denotes hydrogen or C₁ -C₄ -alkyl, and

R₈ denote hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl or cyano.

Preferred dyestuffs are those which, in the form of the free acid, correspond to the formula ##STR3## wherein R₁ ' represents C₁ -C₄ -alkyl or hydrogen,

R₂ ' represents C₁ -C₁₂ -alkyl, phenyl which is optionally substituted by methyl, ethyl, chlorine, methoxy or ethoxy, benzyl, phenethyl, cyclohexyl or methylcyclohexyl,

R₅ ' represents methyl or ethyl,

R₆ ' represents methyl, ethyl or cyanoethyl,

R₈ ' represents hydrogen or chlorine,

R₉ ' represents hydrogen, chlorine, methyl, methoxy or ethoxy, and

R₃ ' represents a direct bond, ##STR4##

The new dyestuffs are prepared by diazotising an amine of the formula ##STR5## in which

X₁, X₂, R₁ and R₂ have the meaning indicated above, and coupling the diazotisation product to coupling components of the formula ##STR6## wherein R₃, R₄, R₅, R₆, R₇, R₈ and R₉ have the meaning indicated above.

The dyestuffs according to the invention are suitable for dyeing natural and synthetic fibre materials, in particular for dyeing polyamide fibres, in level, deep red shades, in particular yellowish-tinged red shades, of very good fastness to light and to wet processing. The new dyestuffs put an expert in the position of being able to produce interesting red shades by combination with, in particular, dyestuffs which dye in bluish-tinged red shades.

The new dyestuffs are already absorbed well onto polyamide fibres in a neutral to weakly acid dyebath. By polyamide fibers there are understood in this context, in particular, those of synthetic polyamides, such as ε-polycaprolactam or condensation products of adipic acids and hexamethylenediamine. The dyestuffs are used either in the form of the free acids or in the form of their salts, in particular their alkali metal salts, preferably the sodium salts or potassium salts, and their ammonium salts.

EXAMPLE 1

4.8 g of 3,4-dichloro-6-(N-methyl-N-phenyl-aminosulphonyl)-aniline are dissolved in 100 ml of glacial acetic acid and 30 ml of concentrated HCl. The solution is cooled to 0° C. The amine is diazotised with 10 ml of a 10% strength NaNO₂ solution and the mixture is subsequently stirred at 0° C. for two hours.

3.6 g of 3-(2-chloro-4-sulphophenoxyacetylamino)-N,N-diethylaniline are introduced into 100 g of ice and 100 g of water. The diazonium salt solution described above is allowed to run into this suspension, and the pH is adjusted to about 4 with sodium acetate solution. The dyestuff of the formula ##STR7## which has precipitated is filtered off and dried at about 50° C.

EXAMPLE 2

5 g of 3,4-dichloro-6-(diisobutylaminosulphonyl)-aniline are diazotised with 10 ml of a 10% strength NaNO₂ solution in 100 ml of glacial acetic acid and 30 ml of concentrated hydrochloric acid at 0° C. The mixture is subsequently stirred at 0° C. for 2 hours.

2.7 g of 3-(sulphophenylacetylamino)-diethyl-aniline are dissolved in 30 ml of 1 N sodium hydroxide solution and the solution is introduced into 100 g of ice and 100 g of H₂ O. The diazonium salt solution described above is allowed to run into this mixture at 0° C. The pH value is then adjusted to about 4 with sodium acetate solution. The dyestuff of the formula ##STR8## which has precipitated is filtered off and dried at 50° C.

DYEING EXAMPLE

0.1 g of the dyestuff from Example 1 is dissolved hot in 100 ml of water, 5 ml of 10% strength ammonium acetate solution are added and the mixture is diluted to a volume of 500 ml with H₂ O. 10 g of polyamide fibres are introduced into the dyebath, the dyebath is brought to the boiling point in the course of 20 minutes, 4 ml of 10% strength acetic acid are added and the bath is boiled for one hour. The fibres are then rinsed and dried at 70° to 80° C. A dyeing is obtained with a yellowish-tinged red shade and with good fastness properties in use, in particular with very good fastness to wet processing.

If the procedure followed is as in Example 1 and 2, using the appropriate diazo components and coupling components, further dyestuffs of the general formula ##STR9## are obtained.

    __________________________________________________________________________     Example                                 Colour shade on                        No.  R.sub.1                                                                              R.sub.2   R.sub.3 Substituent in B                                                                          polyamide                              __________________________________________________________________________     3    Ethyl Phenyl    --CH.sub.2 --O--                                                                       2-Chloro-4-sulpho                                                                         yellowish-tinged red                   4    Methyl                                                                               Benzyl    "       "          "                                      5    iso-Butyl                                                                            iso-Butyl "       "          "                                      6    H     Hexyl     "       "          "                                      7    H     Hexyl     "       2,4-Dichloro-X-                                                                           "                                                                   sulpho                                            8    H     Cyclohexyl                                                                               "       2,4-Dichloro-X-                                                                           "                                                                   sulpho                                            9    Methyl                                                                               Phenyl    "       2,4-Dichloro-X-                                                                           "                                                                   sulpho                                            10   Ethyl Phenyl    "       2,4-Dichloro-X-                                                                           "                                                                   sulpho                                            11   Methyl                                                                               Cyclohexyl                                                                               "       2,4-Dichloro-X-                                                                           "                                                                   sulpho                                            12   Methyl                                                                               Benzyl    "       2,4-Dichloro-X-                                                                           "                                                                   sulpho                                            13   Ethyl Ethyl     "       2,4-Dichloro-X-                                                                           "                                                                   sulpho                                            14   Butyl Butyl     "       2,4-Dichloro-X-                                                                           "                                                                   sulpho                                            15   Butyl Butyl     "       2-Methyl-4-chloro-                                                                         "                                                                  X-sulpho                                          16   Methyl                                                                               Benzyl    "       2-Methyl-4-chloro-                                                                        "                                                                   X-sulpho                                          17   Methyl                                                                               Cyclohexyl                                                                               "       2-Methyl-4-chloro-                                                                        "                                                                   X-sulpho                                          18   H     Butoxypropyl                                                                             "       4-Sulpho   "                                      19   Ethyl Phenyl    "       "          "                                      20   Methyl                                                                               Benzyl    "       "          "                                      21   Ethyl Ethyl     "       "          "                                      22   iso-Butyl                                                                            iso-Butyl "       "          "                                      23   Methyl                                                                               Cyclohexyl                                                                               "       "          "                                      24   Methyl                                                                               Octyl     "       "          "                                      25   Ethyl Phenyl    "       4-Methyl-X-sulpho                                                                         "                                      26   Methyl                                                                               Phenylethyl                                                                              "       "          "                                      27   H     Phenylethyl                                                                              "       "          "                                      28   Methyl                                                                               2-Chlorophenyl                                                                           "       "          "                                      29   H     Hexyl     "       "          "                                      30   Methyl                                                                               4-Methoxyphenyl                                                                          "       "          "                                      31   Ethyl Ethyl     "       "          "                                      32   Ethyl Phenyl    --      4-Methoxy-3-sulpho                                                                        red                                    33   Methyl                                                                               "         --      "          "                                      34   Methyl                                                                               Cyclohexyl                                                                               --      "          "                                      35   Methyl                                                                               Benzyl    --      "          "                                      36   Methyl                                                                               Benzyl    --      3-Sulpho   yellowish-tinged red                   37   Methyl                                                                               Cyclohexyl                                                                               --      "          "                                      38   Methyl                                                                               Phenyl    --      "          "                                      39   Ethyl "         --      "          "                                      40   H     Cyclohexyl                                                                               --      "          "                                      41   H     Octyl     --      "          "                                      42   Methyl                                                                               Phenyl    --      2-Sulpho   scarlet                                43   Ethyl Phenyl    --      "          "                                      44   Methyl                                                                               Benzyl    --      "          "                                      45   "     Cyclohexyl                                                                               --      "          "                                      46   "     4-Methylphenyl                                                                           --      "          "                                      47   "     2-Methoxyphenyl                                                                          --      "          "                                      48   "     Phenyl    --NH--  4-Sulpho   red                                    49   "     Cyclohexyl                                                                               "       "          "                                      50   "     4-Methylphenyl                                                                           "       4-Methoxy-3-sulpho                                                                        "                                      51   Butyl 3-Chlorophenyl                                                                           "       4-Chloro-4-sulpho                                                                         "                                      52   β-Hydroxy-                                                                      4-Ethylphenyl                                                                            "       2-Methyl-4-sulpho                                                                         "                                           ethyl                                                                     53   Ethyl Phenyl    --O--   4-Sulpho   yellowish-tinged                       __________________________________________________________________________                                             red                               

The following table lists examples of other dyestuffs which can be obtained by coupling a diazotised amine of the formula ##STR10## in which

R₁ and R₂ have the meaning indicated in the table, to the coupling components also indicated.

    __________________________________________________________________________                           Coupling            Colour shade on                      Example                                                                             R.sub.1                                                                               R.sub.2   component           polyamide                            __________________________________________________________________________     54   CH.sub.3                                                                              C.sub.3 H.sub.6OC.sub.4 H.sub.9                                                           ##STR11##          yellowish-tinged red                 55   C.sub.4 H.sub.9                                                                       C.sub.4 H.sub.9                                                                           ##STR12##          "                                    56   CH.sub.3                                                                               ##STR13##                                                                                ##STR14##          "                                    57   C.sub.2 H.sub.5                                                                        ##STR15##                                                                                ##STR16##          "                                    58   CH.sub.3                                                                               ##STR17##                                                                                ##STR18##          "                                    59   H                                                                                      ##STR19##                                                                                ##STR20##          "                                    60   CH.sub.3                                                                               ##STR21##                                                                                ##STR22##          "                                    61   C.sub.2 H.sub.4OH                                                                      ##STR23##                                                                                ##STR24##          "                                    62   CH.sub.3                                                                               ##STR25##                                                                                ##STR26##          "                                    63   C.sub.3 H.sub.7                                                                        ##STR27##                                                                                ##STR28##          scarlet                              64   C.sub.2 H.sub.5                                                                       C.sub.4 H.sub.9                                                                           ##STR29##          yellowish-tinged red                 65   H      H.sub.3 C(CH.sub.2).sub.12                                                                ##STR30##          "                                    66   C.sub.2 H.sub.5                                                                        ##STR31##                                                                                ##STR32##          red                                  67   H                                                                                      ##STR33##                                                                                ##STR34##          yellowish-tinged                     __________________________________________________________________________                                               red                             

Other preferred dyestuffs can be obtained by diazotising amines of the formula ##STR35## wherein X₁, X₂, R₁ and R₂ have the meanings indicated in the table which follows,

and coupling the diazotisation products to the coupling components likewise listed in the table.

    __________________________________________________________________________                                           Colour shade on                          Example                                                                             X.sub.1                                                                           X.sub.2                                                                           R.sub.1                                                                           R.sub.2                                                                               Coupling component                                                                              polyamide                                __________________________________________________________________________     68   Cl CF.sub.3                                                                          CH.sub.3                                                                           ##STR36##                                                                             ##STR37##       yellowish-tinged red                     69   Cl CF.sub.3                                                                          CH.sub.3                                                                           ##STR38##                                                                             ##STR39##       yellowish-tinged red                     70   Cl CF.sub.3                                                                          CH.sub.3                                                                           ##STR40##                                                                              "              yellowish-tinged red                     71   Cl CF.sub.3                                                                          CH.sub.3                                                                           ##STR41##                                                                             ##STR42##       red                                      72   Cl CF.sub.3                                                                          H                                                                                  ##STR43##                                                                             ##STR44##       yellowish-tinged red                     73   Cl Br C.sub.4 H.sub.9                                                                   C.sub.4 H.sub.9                                                                         "              yellowish-tinged                                                               red                                      74   CF.sub.3                                                                          Br CH.sub.3                                                                           ##STR45##                                                                             ##STR46##       yellowish-tinged red                     75   CF.sub.3                                                                          Br CH.sub.3                                                                           ##STR47##                                                                             ##STR48##       red                                      76   CF.sub.3                                                                          Cl H                                                                                  ##STR49##                                                                             ##STR50##       yellowish-tinged red                     77   Cl Cl CH.sub.3                                                                           ##STR51##                                                                             ##STR52##       yellowish-tinged red                     __________________________________________________________________________ 

I claim:
 1. Monoazo dyestuffs which, in the form of the free acid, correspond to the formula ##STR53## in which X₁ and X₂ denote chlorine, bromine or trifluoromethyl,R₁ denotes hydrogen or C₁ -C₈ -alkyl, which can be substituted by hydroxyl, R₂ denotes hydrogen, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, C₁ -C₁₃ -alkyl, phenyl which is optionally substituted by methyl, ethyl, chlorine, methoxy or ethoxy, benzyl, phenethyl, cyclohexyl or methylcyclohexyl, R₃ denotes a direct bond, methylene, ethylene, methyleneoxy, methyleneoxycarbonyl, methyleneoxycarbonylamino, aminomethylene or aminoethylene, R₄ denotes hydrogen, methyl, methoxy or ethoxy, R₅ and R₆ denote C₁ -C₄ -alkyl, which can be further substituted by cyano, chlorine, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxycarbonyloxy, C₁ -C₄ -alkylcarbonyloxy or phenylaminocarbonyloxy, benzyl or phenethyl, R₇ denotes hydrogen or C₁ -C₄ -alkyl, and R₈ and R₉ denote hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl or cyano.
 2. Monoazo dyestuffs according to claim 1, which, in the form of the free acid, correspond to the formula ##STR54## wherein R₁ ' represents C₁ -C₄ -alkyl or hydrogen,R₂ ' represents C₁ -C₁₂ -alkyl, phenyl which is optionally substituted by methyl, ethyl, chlorine, methoxy or ethoxy, benzyl, phenethyl, cyclohexyl or methylcyclohexyl, R₅ ' represents methyl or ethyl, R₆ ' represents methyl, ethyl or cyanoethyl, R₈ ' represents hydrogen or chlorine, R₉ ' represents hydrogen, chlorine, methyl, methoxy or ethoxy, and R₃ ' represents a direct bond, --CH₂ -- or --CH₂ --O--. 